EP0174836B1 - Fester starksauerer Katalysator - Google Patents

Fester starksauerer Katalysator Download PDF

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Publication number
EP0174836B1
EP0174836B1 EP85306434A EP85306434A EP0174836B1 EP 0174836 B1 EP0174836 B1 EP 0174836B1 EP 85306434 A EP85306434 A EP 85306434A EP 85306434 A EP85306434 A EP 85306434A EP 0174836 B1 EP0174836 B1 EP 0174836B1
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Prior art keywords
sulfate
catalyst
weight
group viii
support
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EP85306434A
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English (en)
French (fr)
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EP0174836A3 (en
EP0174836A2 (de
Inventor
Shiego C/O Yokkaichi Research Baba
Yukio Yokkaichi Research Shibata
Takahiro Yokkaichi Research Kawamura
Hideo Yokkaichi Research Takaoka
Tsuguo Kimura
Kazuo Kousaka
Yoshihiro Minato
Naruo Hiroshima Technical Institute Yokoyama
Kozo C/O Hiroshima Technical Institute Lida
Tetsuya C/O Hiroshima Technical Institute Imai
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Research Association for Utilization of Light Oil
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Research Association for Utilization of Light Oil
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Priority claimed from JP59188206A external-priority patent/JPS6168137A/ja
Priority claimed from JP59188207A external-priority patent/JPS6168138A/ja
Priority claimed from JP59273481A external-priority patent/JPS61153140A/ja
Priority claimed from JP59273482A external-priority patent/JPS61153141A/ja
Priority claimed from JP60058229A external-priority patent/JPS61220738A/ja
Application filed by Research Association for Utilization of Light Oil filed Critical Research Association for Utilization of Light Oil
Publication of EP0174836A2 publication Critical patent/EP0174836A2/de
Publication of EP0174836A3 publication Critical patent/EP0174836A3/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/226—Catalytic processes not covered by C07C5/23 - C07C5/31 with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2724—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2791—Catalytic processes with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-

Definitions

  • This invention relates to a solid strong acid catalyst and more particularly, it is concerned with a solid strong acid catalyst in which sulfate (SO4) and Group VIII metals of the Periodic Table are supported on a hydroxide or oxide of zirconium and a process for the production of the same.
  • SO4 sulfate
  • Group VIII metals of the Periodic Table are supported on a hydroxide or oxide of zirconium
  • US-A-4 465 788 describes an olefin oligimerization catalyst containing nickel sulfate on a porous support, which is activated by calcining in an oxidising atmosphere, followed by an inert gas treatment at a lower but elevated temperature.
  • the catalyst is not strongly acidic.
  • the reaction temperatures at which this catalyst is used, e.g. 260 o C, is relatively high.
  • DE-A-1 443 496 describes a catalyst for hydrocatalytic treatment of hydrocarbons comprising a hydrogenating/dehydrogenating component, a water-free neutral metal sulfate or water-free cobalt sulfate and an inactive support.
  • the catalyst described is not a strong acid catalyst.
  • a solid strong acid catalyst consisting essentially of a sulfate (SO42 ⁇ ) and at least one Group VIII metal, supported on a support consisting essentially of at least one hydroxide or oxide of zirconium, wherein the Group VIII metal is supported in a proportion of 0.01 to 10 parts by weight to 100 parts by weight of the support.
  • Also provided by the present invention is a process for the production of a solid strong acid catalyst as defined above which process comprises incorporating or applying at least one Group VIII metal and sulfate or a precursor of sulfate in or to a support consisting essentially of a hydroxide or an oxide of zirconium and then calcining and stabilizing.
  • Group VIII metals and sulfate (SO4) or a precursor of sulfate (SO4) is incorporated or applied in or to the support.
  • Group VIII metals include nickel, platinum, ruthenium, rhodium, palladium, osmium and iridium, and the Group VIII metals may be as compounds thereof, and can be incorporated in or applied to the support in conventional manner, for example, by the impregnation method or ion exchange method.
  • the quantity of Group VIII metals to be supported is 0.01 to 10 parts by weight per 100 parts by weight of the support, since if less than 0.01 part by weight, the catalytic effect of the Group VIII metal is decreased and the stability of the activity tends to be insufficient, while if more than 10 parts by weight, the acid strength is lowered thereby decreasing the conversion.
  • sulfate for example, there can be used sulfuric acid, e.g. in a concentration of 0.01 to 10 N, preferably 0.1 to 5 N or ammonium sulfate, e.g. in a concentration of 0.1 to 10 mols.
  • materials capable of forming sulfate after calcining e.g. hydrogen sulfide, sulfur dioxide and sulfur- and halo-containing compounds such as fluorosulfonic acid, sulfuryl chloride or thionyl chloride, or a mixture thereof.
  • introduction of the Group VIII metal and sulfate may be carried out by any known method, for example.
  • a Group VIII metal is introduced or applied to the support, which is then treated with an agent containing sulfate, calcined and stabilized, thus preparing a solid strong acid catalyst.
  • Group VIII metals for example, platinum can be introduced or applied by an aqueous solution of chloroplatinic acid or tetrammine platinum complex and thereafter, a sufficient catalytic property can be given by only a drying treatment prior to the treatment with a sulfate-containing agent.
  • sulfuric acid with a concentration of 0.01 to 10 N, preferably 0.1 to 5 N or ammonium sulfate with a concentration of 0.1 to 10 mols may be used in a quantity of 1 to 10 times as much as the catalyst by weight, and other compounds capable of forming sulfate after a calcining treatment, such as hydrogen sulfide, sulfur dioxide and sulfuryl chloride can of course be used with similar effects.
  • Group VIII metals and sulfate can be also carried out by the use of at least one sulfate of a Group VIII metal.
  • the sulfate of Group VIII metals include, for example, nickel sulfate, platinum sulfate, palladium sulfate, ruthenium sulfate and nickel ammonium sulfate.
  • the sulfates of Group VIII metals can be incorporated or applied by any method, e.g. impregnation using an aqueous solution, for example, nickel sulfate.
  • calcination in air can be carried out at a temperature of, for example, 50 to 550 o C, preferably 100 to 400 o C for, e.g., 1 to 24 hours, but for the present invention, it is important for good results to effect a calcining and stabilizing treatment at a temperature of 450 to 800 o C, preferably 500 to 650 o C for 0.5 to 10 hours in an oxidizing atmosphere after the treatment with the sulfate-containing agent.
  • the catalyst is given a strong acidity.
  • the calcining and stabilizing treatment is carried out in a reducing atmosphere, the catalytic activity is lowered to a great extent probably due to change of the bonding state of the sulfate on the Group VIII metal or compound thereof, or to reduction and decomposition thereof. This is not favourable.
  • the support can be subjected firstly to the treatment with a sulfate-containing agent and then to incorporation or application of a Group VIII metal as it is or after a calcining treatment at a temperature of 50 to 600 o C. After the Group VIII metal is incorporated or applied, it is necessary to calcine and stabilize the catalyst at a temperature of e.g. 450 to 800 o C for e.g. 0.5 to 10 hours in an oxidizing atmosphere.
  • Catalysts prepared in this way may exhibit an excellent catalytic activity under flow of hydrogen. That is to say, it is considered that a Group VIII metal acts as a center of supplying active hydrogen for solid strong acid sites formed of sulfate and a metal oxide surface.
  • a reduction procedure at lower than 400 o C was preferred, but is not always necessary for this catalyst. Through this procedure, there is found no generation of hydrogen sulfide, etc. due to reduction of sulfate under flowing of hydrogen. Thus, it is assumed that sulfate is firmly bound with the catalyst surface by effecting the calcining and stabilizing treatment in the final step of the process for preparing the catalyst, and a stable strong acid catalyst may thus be formed.
  • the catalyst prepared according to the process of the present invention is useful for various reactions, in particular, isomerization of hydrocarbons. That is, various useful products can selectively be obtained by the use of the catalyst according to the present invention for skeletal isomerization of paraffinic hydrocarbons, isomerization of cyclic compounds, e.g. obtaining cyclohexane from methylcyclopentane, isomerization of aromatic compounds, e.g. obtaining p-xylene from m-xylene.
  • the above described isomerization reactions are preferably carried out at a reaction temperature of 400 °C or lower, since if the reaction is carried out at a temperature of higher than 400 °C, in particular, in the presence of hydrogen, sulfate (SO4) tends to be decomposed to lower the acid strength of the catalyst so that the isomerization does not proceed as at a lower temperature.
  • SO4 sulfate
  • the catalyst of the present invention which is highly active at a lower temperature is particularly useful for skeletal isomerization reaction of light petroleum fractions in order to obtain higher octane number products because the thermodynamic equilibrium of light paraffinic hydrocarbons shows that the presence of higher octane number components - highly branched paraffins - are advantageous at a lower temperature.
  • a feed oil of an octane number of 60-70 containing 50 to 80 % of paraffinic hydrocarbons such as n-pentane and n-hexane, known as light naphtha fractions can selectively be converted into a useful oil as a gasoline fraction of an octane number of 80-90 in the presence of a catalyst of the present invention at a temperature of 400 °C or lower, preferably 70 to 250 °C, a pressure of 1 to 50 bar, a liquid space velocity of 0.5 to 10 hr ⁇ 1 and a hydrogen to feed oil molar ratio of 1 to 10.
  • Support A was impregnated with aqueous solutions of chloroplatinic acid, palladium chloride, nickel nitrate, ferric nitrate, cobalt nitrate, ruthenium chloride and rhodium chloride respectively, dried at 110 °C for a whole day and night, added to 650 g of 1 N sulfuric acid, the excess of which was separated by filtration, and calcined at 600 °C for 3 hours to obtain Catalysts 1 to 7.
  • the solid acid strength was determined by the titration method using a Hammett indicator in a benzene solvent to obtain results as shown in Table 1.
  • Support A prepared in an analogous manner to Example 1 was immersed in an aqueous solution of chloroplatinic acid with such a concentration as to give 0.5 part by weight as platinum metal per 100 parts by weight of the support weight, dried at 110 °C and calcined at 600 °C for 3 hours to obtain Comparative Catalyst 1.
  • the solid acid strength was determined by the titration method using a Hammett indicator in a benzene solvent to obtain results as shown in Table 1.
  • Support A prepared in an analogous manner to Example 1 was dried at 110 °C, added to 1 N sulfuric acid the excess of which was then separated by filtration, dried at 110 °C and then calcined at 600 °C for 3 hours to obtain Comparative Catalyst 2.
  • the solid acid strength was determined by the titration method using a Hammett indicator in a benzene solvent to obtain results as shown in Table 1.
  • Support A of Example 1 300 g was added to 650 g of 1 N sulfuric acid the excess of which was separated by filtration, dried at 110 °C for one day and night to give Support G and then calcined at 600 °C for 3 hours to prepare Support H.
  • Supports G and H were respectively immersed in an aqueous solution of chloroplatinic acid with such a concentration as to give 0.5 part by weight as platinum metal to 100 parts by weight of the support, dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours to prepare Catalysts 13 and 14.
  • Support G was immersed in aqueous solutions of palladium chloride, rhodium chloride and ruthenium chloride respectively, dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours to prepare Catalysts 15, 16 and 17 each having 0.5 part by weight of palladium, rhodium and ruthenium per 100 parts by weight of the support.
  • Support G was immersed in aqueous solutions of ferric nitrate, cobalt nitrate and nickel nitrate respectively, dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours to prepare Catalysts 18, 19 and 20 supporting each 2 parts by weight of ferric oxide, cobalt oxide and nickel oxide per 100 parts by weight of the support.
  • Example 1 was immersed in an aqueous solution of nickel sulfate with such a concentration as to give 5.0 parts by weight as nickel metal to 100 parts by weight of the support, dried at 110 °C for a whole day and night and then calcined at 550 °C, 600 °C, 650 °C, 700 °C and 800 °C for 3 hours to prepare Catalysts 25 to 29.
  • Example 1 was immersed in an aqueous solution of palladium sulfate, aqueous sulfuric acid solution of chloroplatinic acid and aqueous sulfuric acid solution of rhodium chloride, dried at 110 °C for a whole day and night and then calcined at 575 °C for 3 hours to prepare Catalysts 32 to 34 supporting respectively 0.5, 0.01 and 0.5 part by weight of palladium, platinum and rhodium per 100 parts by weight of the support.
  • the solid acid strength was determined by the titration method using a Hammett indicator in a solvent of benzene to obtain results as shown in Table 3.
  • Example 1 300 g of Support A of Example 1 was immersed in an aqueous solution of chloroplatinic acid, palladium chloride, nickel nitrate, ferric nitrate, cobalt nitrate, ruthenium chloride or rhodium chloride, dried at 110 °C for a whole day and night, added to 500 ml of a solution of sulfuryl chloride (reagent chemical grade, manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.), dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours to prepare Catalysts 35 to 41.
  • chloroplatinic acid palladium chloride
  • nickel nitrate nickel nitrate
  • ferric nitrate ferric nitrate
  • cobalt nitrate ruthenium chloride or rhodium chloride
  • the solid acid strength thereof was measured by the titration method using a Hammett indicator in a solvent of benzene to obtain results as shown in Table 4.
  • Example 1 was immersed in an aqueous solution of commercially available sulfuryl chloride (manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.), dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours to prepare Comparative Catalyst 3.
  • the solid acid strength was measured by the titration method using a Hammett indicator in a benzene solvent to obtain results as shown in Table 4.
  • Support A of Example 1 300 g was immersed in 600 ml of a solution of commercially available sulfuryl chloride (reagent chemical grade, manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.), dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours to prepare Support J.
  • sulfuryl chloride reagent chemical grade, manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.
  • Support I and J were immersed respectively in an aqueous solution of chloroplatinic acid with such a concentration as to give 0.5 part by weight as platinum metal to 100 parts by weight of the support, dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours to prepare Catalysts 47 and 48.
  • Support I was immersed in aqueous solutions of palladium chloride, rhodium chloride and ruthenium chloride respectively, dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours to prepare Catalysts 49 to 51 each supporting 0.5 part by weight of palladium, rhodium and ruthenium per 100 parts by weight of the support.
  • Support I was immersed in aqueous solutions of ferric nitrate, cobalt nitrate and nickel nitrate respectively, dried at 110 °C for a whole day and night and then calcined at 600 °C for 3 hours, thus preparing Catalysts 52 to 54 supporting respectively 2 parts by weight of iron oxide, cobalt oxide and nickel oxide per 100 parts by weight of the support.
  • Catalysts 1, 13, 26, 27, 29, 35 and 47 prepared in Examples 1 to 5 and Comparative Catalysts 1 to 3 prepared in Comparative Examples 1 to 3 were respectively shaped in pellets with a diameter of 0.59-1.00 mm.
  • hydroisomerization reaction of n-pentane was carried out in a high pressure flow reactor with a length of 22 cm and inner diameter of 1 cm under the following reaction conditions: Temperature 200 °C Total Pressure 10 bar H2/n-Pentane Molar Ratio 5/1 mol/mol Liquid Space Velocity 1.5 ml n-pentane/ml catalyst/hr
  • catalysts prepared according to the present invention are excellent catalysts having higher activities for the skeletal isomerization of n-pentane and longer catalyst life, which result from the presence of Group VIII metals and sulfate.
  • Catalysts 1 and 35 each being shaped in pellets with a diameter of 0.59-1.00 mm, hydroisomerization reaction of n-hexane was carried out in a high pressure flow reactor with a length of 22 cm and inner diameter of 1 cm under the following reaction conditions. Before the reaction, the catalysts were subjected to reduction with hydrogen at 300 °C for 2 hours to stabilize the catalytic activity. The amounts of sulfate supported on Catalysts 1 and 35 were 6.5 and 18.5 % by weight on the fresh catalysts, and 6.3 and 17.2 % by weight on the used catalysts, respectively.
  • Example 1 10 g of Support A of Example 1 was immersed in an aqueous solution of chloroplatinic acid with such a concentration as to give 0.5 part by weight as platinum metal to 100 parts by weight of the support, dried at 110 °C for a whole day and night, then treated with N2 gas containing 20 % of SO2 flowing at a rate of 50 Nl.hr at 300 °C for 3 hours and calcined at 550 °C for 1 hour to prepare Catalyst 67.
  • chloroplatinic acid with such a concentration as to give 0.5 part by weight as platinum metal to 100 parts by weight of the support, dried at 110 °C for a whole day and night, then treated with N2 gas containing 20 % of SO2 flowing at a rate of 50 Nl.hr at 300 °C for 3 hours and calcined at 550 °C for 1 hour to prepare Catalyst 67.
  • Catalyst 67 200 mg was packed in a pulse reactor and isomerization reaction of n-butane was then carried out by feeding 1 ml of N2 gas containing 10 % of n-butane to the pulse reactor at 300 °C in helium stream.
  • the outlet gas of the pulse reactor was subjected to analysis by gas chromatography to obtain a conversion of 52.0 % and isomerization of 60.5 % (defined similarly to Example 9).
  • Catalyst 1 was shaped in pellets with a diameter of 0.59 to 1.00 mm. Using this catalyst, hydroisomerization reaction of methylcyclopentane was carried out in a high pressure flow reactor with a length of 22 cm and an inner diameter of 1 cm under the following reaction conditions: Temperature 200 °C Total Pressure 10 bar H2/Methylcyclopentane Molar Ratio 5/1 mol/mol Liquid Space Velocity 1.5 ml methylcyclopentane/ml catalyst/hr The composition of the reactor outlet gas was analyzed by gas chromatography to obtain methylcyclopentane 48 wt %, cyclohexane 24 wt % and other hydrocarbons 28 wt %.
  • the catalyst of the present invention is also useful for the isomerization reaction of methylcyclopentane to cyclohexane.
  • Catalyst 35 of Example 4 was further calcined at 600 °C for 3 hours to prepare Catalyst 68, which powder was shaped in pellets with a diameter of 0.59 to 1.00 mm.

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Claims (11)

  1. Fester, stark saurer Katalysator, welcher im wesentlichen besteht aus einem Sulfat (SO₄²⁻) und wenigstens einem Metall der Gruppe VIII des Periodensystems der Elemente und welcher auf einem Träger aufgezogen ist, der im wesentlichen besteht aus wenigstens einem Hydroxid oder Oxid von Zirkonium, worin das Metall der Gruppe VIII des Periodensystems der Elemente auf dem Träger in einem Verhältnis von 0,01 bis 10 Gew.-Teilen auf 100 Gew.-Teile des Trägers aufgezogen ist.
  2. Fester, stark saurer Katalysator nach Anspruch 1, worin das Metall der Gruppe VIII des Periodensystems der Elemente eines oder mehrere Metall(e) der Gruppe Nickel, Platin, Eisen, Cobalt, Ruthenium, Rhodium, Palladium, Osmium und Indium ist/sind.
  3. Verfahren zur Herstellung eines festen, stark sauren Katalysators nach Anspruch 1 oder Anspruch 2, welches das Einbringen oder Aufbringen von wenigstens einem Metall der Gruppe VIII des Periodensystems der Elemente und von Sulfat oder einer Vorstufe von Sulfat in oder auf einen Träger, der im wesentlichen besteht aus einem Hydroxid oder einem Oxid von Zirkonium, sowie das anschließende Calcinieren und Stabilisieren umfaßt.
  4. Verfahren nach Anspruch 3, worin das Sulfat Schwefelsäure oder Ammoniumsulfat ist.
  5. Verfahren nach Anspruch 3, worin die Vorstufe von Sulfat Hydrogensulfid oder Schwefeldioxid oder Sulfurylchlorid, Thionylchlorid, Fluorsulfonsäure oder eine Mischung davon ist.
  6. Verfahren nach irgendeinem der Ansprüche 3 bis 5, worin das Calcinieren und Stabilisieren bei einer Temperatur von 450 ° bis 800 °C durchgeführt werden.
  7. Verfahren nach irgendeinem der Ansprüche 3 bis 6, worin Sulfat nach dem Calcinieren und Stabilisieren in einem Verhältnis von 0,1 bis 25 Gew.-Teile auf 100 Gew.-Teile des Trägers eingebracht oder aufgebracht wird.
  8. Verfahren nach irgendeinem der Ansprüche 3 bis 7, worin das Einbringen oder Aufbringen des Metalls der Gruppe VIII des Periodensystems der Elemente durch Imprägnieren oder Ionenaustausch erfolgt.
  9. Verfahren nach irgendeinem der Ansprüche 3 bis 8, worin das Sulfat eingebracht oder aufgebracht wird unter Verwendung 0,01- bis 10 N Schwefelsäure oder 0,1 bis 10 Mol Ammoniumsulfat in einer Menge vom 1- bis 10-fachen des Gewichts des Katalysators.
  10. Verfahren nach irgendeinem der Ansprüche 3 bis 9, worin das Sulfat eines Metalls der Gruppe VIII des Periodensystems der Elemente eine oder mehrere Verbindung(en) aus der Gruppe Nickelsulfat, Platinsulfat, Palladiumsulfat, Rutheniumsulfat oder Nickelammoniumsulfat ist/sind.
  11. Verwendung eines Katalysators nach Anspruch 1 oder Anspruch 2 oder eines nach einem Verfahren gemäß irgendeinem der Ansprüche 3 bis 10 hergestellten Katalysators zum Katalysieren der Isomerisierung von Kohlenwasserstoffen, der Gerüstisomerisierung von paraffinischen Kohlenwasserstoffen, der Crackung von Kohlenwasserstoffen oder der Alkylierung von Kohlenwasserstoffen.
EP85306434A 1984-09-10 1985-09-10 Fester starksauerer Katalysator Expired - Lifetime EP0174836B1 (de)

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JP59188206A JPS6168137A (ja) 1984-09-10 1984-09-10 固体酸触媒の製造方法
JP188207/84 1984-09-10
JP59188207A JPS6168138A (ja) 1984-09-10 1984-09-10 固体酸触媒の製造方法
JP188206/84 1984-09-10
JP59273481A JPS61153140A (ja) 1984-12-26 1984-12-26 固体酸触媒の製造方法
JP273482/84 1984-12-26
JP59273482A JPS61153141A (ja) 1984-12-26 1984-12-26 固体酸触媒の製造方法
JP273481/84 1984-12-26
JP58229/85 1985-03-25
JP60058229A JPS61220738A (ja) 1985-03-25 1985-03-25 固体強酸触媒の製造方法

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EP0174836A3 (en) 1987-04-29
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US5120898A (en) 1992-06-09
US5036035A (en) 1991-07-30

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